Method and apparatus for producing cyanogen chloride by spray reaction means



March 3',- 1970 Y. s. SURYANARAYANA ETAL 3,498,761 METHOD AND APPARATUS FOR PRODUCING CYANOGEN CHLORIDE BY SPRAY REACTION MEANS Filed March 10, 196"! (I O Lu (\J CD 2 [E I i= R :'FF;\-E U \D #0 O I 6% 3 gm 5 a IT 9 u (\1 Q N LL- 1 1 3 g N 5 I A 9 D 56 g 1:? V 6 z \J U (\l I U E 3 -INVENTOR R O YELAGONDAHALLY s. SURYANARAYANA WILLIAM S-DURRELL {R D 4 9' u) 0 1, BY MW, N U 5' M ATTORNEYS United States Patent 0 METHOD AND APPARATUS FOR PRODUCING CYANOGEN CHLORIDE BY SPRAY REAC- TION MEANS Yelagondahally Subramaniam Suryanarayana and William Sandford Durrell, Mobile, Ala, assignors to Geigy Chemical Corporation, Ardsley, N.Y.

Filed Mar. 10, 1967, Ser. No. 622,332 lint. Cl. C(llc 3/00; C07c 119/00 U.S. Cl. 23359 4 Claims ABSTRACT OF THE DISCLOSURE Hydrogen cyanide and chlorine are mixed to produce a gaseous mixture in a vaporizer, and the gaseous mixture is dispersed in a spray chamber and water is sprayed into the spray chamber, the amount of water being controlled so that the resulting hydrochloric acid is at a concentration of about 10%. If necessary to complete the reaction, the cyanogen chloride, unreacted hydrogen cyanide vapor and chlorine are passed into a cooled reactor partially flooded with hydrochloric acid at a concentration of about 10-20% and chlorine stripped from the hydrochloric acid produced in the spray chamber is also fed to the reaction column.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a method and apparatus for the production of cyanogen chloride, and more particularly it relates to the production of cyanogen chloride by spraying water into a gaseous mixture of hydrogen cyanide and chlorine whereby the by-product acid is at Description of the prior art A presently used commercial process of preparing cyanogen chloride for conversion into cyanuric chlo ride is described in U.S. Patent 3,197,273 in the name of Elwood Bruce Trickey. In this process, chlorine and hydrogen cyanide are charged into the reaction section of a packed column having a purification, washing or scrubbing section, a reaction section, and a stripping section. Water is fed in at the top of the scrubbing section and steam is introduced at the base of the column at the bottom of the stripping section. By maintaining the proper rates of feed of the various materials, the temperature and conditions in the column can be maintained such that a high yield of cyanogen chloride is obtained as a gas at the top of the reactor.

The process of this patent, while it is quite satisfactory with respect to the quality and amount of the product which it is desired to produce, also produces at the bottom of the reactor column a by-product of dilute, i.e. 23% aqueous hydrochloric acid. This by-product is relatively easily disposed of when the quantity thereof is small, but in actual practice the amounts produced are so great that they cannot be disposed of simply by discharging into a stream or river without exceeding the amount which can be so discharged as established by pollution control standards. The alternative of concentrating the dilute hydrochloric acid and using it in other processes or selling it is not economically feasible, since the costs of conice centrating the dilute acid are greater than purchasing concentrated acid from commercial sources.

Production of the cyanogen chloride under conditions which would produce the by-product aqueous hydrochloric acid at higher concentrations have heretofore appeared to be an unlikely solution to the problems of by-product disposal or by-product recovery, because of the twin problems of intolerable, from the commercial standpoint, losses of the product cyanogen chloride by hydrolysis and directly from the bottom of the reaction column along with the by-product hydrochloric acid. The necessity to keep hydrolysis losses low and substantially eliminate loss of cyanogen chloride are essential to the successful commercial production of cyanogen chloride. A third essential condition is the prevention of the formation of NCl which is extremely explosive and therefore an undesired reaction product not only from the standpoint of loss of the primary product but also from the standpoint of safety.

SUMMARY OF THE INVENTION The present invention relates to a method and apparatus for overcoming the problems described above and carrying out the reaction of chlorine and hydrogen cyanide to produce cyanogen chloride by feeding the two raw materials as a gaseous mixture into a spray chamber and spraying water into the spray chamber. By carefully controlling the conditions, a high rate of conversion to cyanogen chloride can be achieved at low hydrolysis losses and production of aqueous hydrochloric acid in concentrations up to about 10%. The reaction can be carried nearer to completion by passing the stripped bottoms from the spray chamber in countercurrent flow to the gaseous output from the spray chamber, and the bottoms from such a reaction apparatus will be near 20% hydrochloric acid.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in connection With the accompanying drawings, in which:

FIG. 1 is a schematic view of an experimental apparatus including a spray chamber arranged to carry out the novel steps of the method of the present invention; and

FIG. 2 is a schematic view of a practical apparatus for carrying out the method of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, an experimental apparatus for carrying out the essential steps of the method of the present invention comprises a vaporizer 10 having a liquid hydrogen cyanide inlet 11 and a gaseous chlorine inlet 12. By application of external heat the liquid HCN is vaporized in the vaporizer. The outlet 13 from the vaporizer is connected to a gas dispersing head 14 in a spray chamber 15 into which extends a water inlet 16 having a spray nozzle 17 on the end thereof. Gaseous reaction products leave the spray chamber through a gas outlet 18 and liquid reaction products leave the spray chamber through the liquid outlet 19.

In operation, liquid HCN is pumped into the vaporizer 10 and gaseous chlorine at ambient temperature is pumped into the vaporizer and the HCN is vaporized and mixed with the chlorine. The resulting mixture is dispersed into the spray chamber 15 through the gas dispersing head 14 and water is sprayed into the gaseous mixture through the nozzle 17 in a spray of very fine droplets. The reaction goes nearly to completion in the spray chamber, and the gaseous cyanogen chloride mixed with unreacted HCN and chlorine passes off through the gas outlet 18 while aqueous hydrochloric acid in concentrations up to 10% is removed from the bottom of the spray chamber.

The amounts of chlorine, HCN and water are controlled so that the reaction produces aqueous hydrochloric acid as a by-product at a concentration of about A specific example will be given in order to show the manner of carrying out the invention.

EXAMPLES 1 AND 2 Liquid HCN was fed to the vaporizer, and chlorine was fed into the vaporizer at ambient temperature and in an amount sufficient to give an excess of 10% over that needed for complete reaction with the HCN. The resulting vapor, which was a mixture of HCN and chlo rine,.was dispersed into a spray chamber which was 9" in diameter and 18" high. Water was sprayed into the chamber from above in a spray of fine droplets. The amounts of HCN and Water are given below in runs 1 and 2 in Table I. The resulting gaseous product was dried and the amount of CNCl contained therein measured. The concentration of the liquid acid which remained in the bottom of the spray chamber was also measured.

TABLE I Equivalent Run Liquid HCN, Water, HCN solu- Percent HCN No. qmJmin. ccJmin. tion, percent conversion diameter. Liquid HCN is fed into the vaporizer through an HCN inlet 21, and part of the chlorine isfed into the vaporizer through a chlorine inlet 22. The remainder of the chlorine is by-passed through a by-pass line 24 which joins the vapor line from the vapor outlet 23 from the vaporizer.

Two spray chambers 25 are provided, each of which is wide and high, and made of stoneware. Each chamber has five nozzles 26 therein which are fixed to an 8' diameter ring 27 placed at the center of the top of thechamber. A gas dispersion means 28 is positioned in the bottom of each chamber on the end of the HCN- chlorine feed line. A water supply pipe 29 leads to each set of water spray nozzles 27.

Each spray chamber has a gas outlet near the top thereof from which a gas line 30 extends to a separator 31 for separating liquid from the gas, and from the separator 31 a line leads to each of two 30" diameter packed columns 32 having a heat exchanger ,in the middle thereof. The columns 31 each have an upper packed section 12 ft. long and a lower packed section 9 ft. long, both sections being packed with /2" saddles. The heat exchanger section is 9 ft. long and has 109 1 /2 tubes therein. The outlet line from the separator 31 enters each of the packed columns just below the heat exchanger section.

Each spray chamber also has a liquid outlet near the bottom thereof from which the liquid line 33 leads to a reboiler 34. The reboiler is supplied with steam by lines (not shown) and heats the bottoms from the spray chambers 25 to drive 01? the chlorine therefrom, and a chlorine line 35 extends from the reboiler to the line between the separator 31 and the packed columns 32. An HCl line extends from the reboiler through a pump 36 and a cooler 37 and branches to the top of each of the columns 32.

A gas outlet line 38 is provided at the top of each column 32, and a bottom line 39- leads from the bottom of each column 32 to a second reboiler 40, which is also steam heated by a steam supply (not shown). The chlorine line from the second reboiler leads back into the lower packed section of each column 32, and an acid line from the bottom of the second reboiler.

It is contemplated that by feeding 1,065 lbs./hr. HCN and vaporizing it with 1,841 lbs./hr. chlorine, and bypassing about 3,445 lbs/hr. of the chlorine, and by spraying water into the spray chambers at a rate of 5,286 lbs./hr., the apparatus can produce 3,066 lbs/hr. CNCl. Under these conditions, the cooling water should enter the heat exchanger part of the columns 32 at about 25 C. and leave at 28 C., and the temperature of the liquid ta the bottom of the heat exchanger sections is about 50 C. and at the top is about C.

What is claimed is:

1. A method of producing cyanogen chloride, comprising the steps of preparing a gaseous mixture of hydrogen cyanide and chlorine in at least stoichiometric pro portions for reaction to cyanogen chloride and at a temperature at which both are in gaseous form, and spraying water at ambient temperature into said gaseous mixture to produce gaseous cyanogen chloride and aqueous hydrochloric acid, the amount of Water being sufiicient to produce the hydrochloric acid at a concentration of at least 10%, and recovering the cyanogen chloride.

2. A method as claimed in claim 1 in which the amounts of hydrogen cyanide, chlorine and Water are supplied in quantities such that the chlorine is in excess of that needed for a complete reaction with the hydrogen cyanide by about 10%.

3. A method as claimed in claim 1 in which the step of preparing the gaseous mixture of hydrogen cyanide and chlorine comprises vaporizing liquid hydrogen cyanide and mixing the vapor with about half of the required quantity of chlorine in gaseous form, and feeding the remainder of the gaseous chlorine into the mixed hydrogen cyanide and gaseous chlorine.

4. A method as claimed in claim 1 and further comprising the step of passing the gaseous reaction product from the spraying step countercurrent to an aqueous hydrochloric acid medium having an outlet concentration of about 20%, while at the same time removing the free chlorine from the hydrochloric acid produced in said spray step and also passing it through the hydrochloric acid medium, whereby the reaction between the hydrogen cyanide and chlorine is more nearly completed.

References Cited UNITED STATES PATENTS 2,672,398 3/1954 Huemer et al 23-359 3,011,864 12/1961 Morse et al 23359 3,197,273 7/1965 Trickey 23359 OSCAR R. VERTIZ, Primary Examiner H. S. MILLER, Assistant Examiner US. Cl. X.R. 2375, 154, 284 

